The attack on Vinnytsia, far from the war's frontlines, occurred in mid-morning when the streets were full of people. It appeared to hit a business centre, setting cars on fire and sending plumes of thick black smoke over the city.
A Russian submarine in the Black Sea fired Kalibr cruise missiles at the city, the deputy head of Ukraine's presidential office, Kyrylo Tymoshenko, wrote on the Telegram messaging app.
The Russian military has not confirmed the strike, but Margarita Simonyan, head of the state-controlled Russian television network RT, said on her messaging-app channel that military officials had told her a building in Vinnytsia was targeted because it housed Ukrainian "Nazis".
Vinnytsia is one of Ukraine's largest cities, with a population of 370,000. Thousands of people from eastern Ukraine, where Russia has concentrated its offensive, have fled there since the start of the war.
Ukraine's national police chief, Ihor Klymenko, said only six of the dead have been identified so far, while 39 people are still missing. Of the 52 people taken to hospital, five remain in critical condition while 34 sustained severe injuries, a regional healthcare department official told Associated Press.
The missiles ignited a fire that spread to engulf 50 cars in an adjacent car park, officials said.
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